Novel n-haloalkylated anilines

ABSTRACT

NOVEL N-HALOALKYLATED ANILINES PREPARED BY REACTION OF N-ALKENYL ANILINES WITH HYDROGEN HALIDE USEFUL FOR THE CONTROL OF INSECTS.

United States Patent 3,787,478 NOVEL N-HALOALKYLATED ANILINES LadislavDolejs, Pavel Beran, Karel Slama, and Frantisek Sorm, Prague,Czechoslovakia, assignors to Ceskoslovenska Akademie Ved, Prague,Czechoslovakia No Drawing. Filed Apr. 21, 1971, Ser. No. 136,221 Claimspriority, application Czechoslovakia, May 5, 1970, 3,122/ 70 Int. Cl.C07c 101/58 US. Cl. 260-471 R 13 Claims ABSTRACT OF THE DISCLOSURE NovelN-haloalkylated anilines prepared by reaction of N-alkenyl anilines withhydrogen halide useful for the control of insects.

This invention relates to the novel compounds of Formula I:

wherein,

-( J0 R or -ii-R in which R is hydrogen, lower alkyl, aryl or aralkyl; Yis hydrogen, or together with X, forms the methylenedioxy bridge; R isone of the groups (A), (B) or (C):

R 1] R(:CH(CH2)3CCH(CH2)T i Z Z Z3 z Z1 in which each of R, R, R and Ris hydrogen or lower alkyl; Z is hydrogen and Z is hydrogen, bromo,chloro,

fluoro, or, together with Z, a carbon-carbon bond; Z is hydrogen and Zis hydrogen, bromo, chloro, fluoro, or together with Z a carbon-carbonbond; Z is bromo, chloro or fluoro;

R is hydrogen, methyl, ethyl, propyl, n-butyl or one of the groups (A),(B) or (C);

m is the positive integer one or two; and n is the positive integer twoor three.

The term aryl, as used herein, refers to an aryl group of six to twelvecarbon atoms, such as phenyl, naphthyl and methylphenyl.

The term lower alkyl, as used herein, refers to an alkyl group, straightor branched, having a chain length of one to six carbon atoms. The termaralkyl, as used herein, refers to aralkyl of seven to twelve carbonatoms, such as benzyl, phenethyl, methylbenzyl and naphthylmethyl.

The novel compounds of Formula I are useful for the control of insects.The utility of these compounds as insect control agents is believed tobe attributable to their juvenile hormone activity. They are preferablyapplied to the immature insect, namely-during the embryo, larvae orpupae state in view of their ability to inhibit metamor- 3,787,478Patented Jan. 22, 1974 e CC phosis and otherwise cause abnormaldevelopment. These compounds are effective control agents forHemipteran, such as Lygaeidae, Miridae and Pyrrhocoridae; Coleopteran;Lepidopteran, such as Pyralidae, Noctiidae and Gelechiidae; Dipteran,such as mosquitoes; Orthoptera, such as roaches; and Homoptera, such asaphids. The compounds can be applied at low dosage levels of the orderof 0.001 g. to 25 g. per insect. Suitable carrier substances includeliquid or solid carriers, such as water, mineral or vegetable oils,talc, silica and natural or synthetic resin. The control of insects inaccordance with the present invention is accomplished by spraying,dusting or exposing the insects to the vapor of the novel compounds.Generally, a concentration of less than 50% of the active compound isemployed. The formulation can include insect attractants, emulsifyingagents and wetting agents to assist in the application and efficiency ofthe active ingredient.

In the description following, each of X, Y, R to R Z to Z m and n are asdefined above unless otherwise indicated.

The compounds of Formula I are prepared by treatment of thecorresponding unsaturated aniline (II) with hydrogen halide in anorganic solvent such as an ether, alcohol, carbon tetrachloride, and thelike (the broken line in wherein R is one of the groups A, B or C and Ris hydrogen, methyl, ethyl, propyl, n-butyl or one of the groups (A'),(B) or (C'):

Rs R4 R The precursors Formula II can be prepared as described inapplication Ser. No. 98,093, filed Dec. 14, 1970, the disclosure ofwhich is incorporated by reference.

The following examples are provided to illustrate the present invention.

EXAMPLE 1 Ethyl N,N-bis-(7-chloro-3,7-dimethy1 2octenyl)-paminobenzoate. Ethyl N,N-digeranyl-p-aminobenzoate isdissolved in an anhydrous solvent (ether, alcohol) and the solution issaturated with dry gaseous hydrogen chloride. The reaction mixture isallowed to stand at ordinary temperature for one hour, the solvent isevaporated under diminished pressure at a lower temperature, and theresidue is shaken with a mixture of ether and aqueous sodium hydrogencarbonate. The ethereal layer is washed with water and dried over sodiumsulfate. The yield is quantitative, the product contains only traces ofthe starting material which may be removed by chromatography on a layerof silica gel. Mass spectrum: The molecular ion shows a negligibleintensity (M 509 for C H NO Cl characteristic ions MHCl, MZHCl, m/ e368, 301, 178, 165, 120.

EXAMPLE 2 Ethyl N- (7-fluoro-3,7-dimethyl-Z-octenyl) p aminobenzoate.-Asolution of N-geranyl-p-aminobenzoic acid ethyl ester in a dry solvent(e.g., in ether or alcohol) is placed into a poly (ethylene) vessel andtreated under cooling with excess liquid hydrogen fluoride. The reactionmixture is allowed to stand in an ice-box for 2 days andf thencautiously neutralized under cooling with dilute alkali hydroxide. Themixture is thoroughly shaken, the organic layer is separated, dried, andthe solvent is evaporated. The residue is chromatographed on a column ofsilica gel. Mass spectrum: Characteristic peaks at 321, 301, 178, 165,and 150.

EXAMPLE 3 Each of the unsaturated compounds under column (I) is used asthe starting material in the process of Example 1 to prepare therespective chloride under column (II).

ethyl N-3,7-dimethyloct-6-enyl-p-aminobenzoate ethylN-1,S-dimethylhex-4-enyl-p-aminobenzoate ethylN-3,7-dimethylnona-2,6-dienyl-p-aminobenzoate ethylN-3-ethyl-7-methylnona-2,fi-dienyl-p-aminobenzoate ethylN-4,8-dimethylnona-3,7-dienyl-p-aminobenzoate methylN-3,7-dimethylocta-2,6-dienyl p-aminophenylketone methylN-3,7-dimethyloct-6-enyl p-aminophenylketoneN-3,7-dimethylocta-2,6-dienyl 3,4-methylenedioxyanilineN-3,7-dimethyloct-6-enyl 3,4-methylenedioxyanilineN-l,5-dimethylhex-4-enyl 3,4methylenedioxyanilineN-3,7-dimethylnona-2,6-dienyl 3,4-methylenedioxyaniline'N-3-ethyl-7-methylnona-2,6-dienyl 3,4-methylenedioxyanilineN-4,8-dimethylnona-3,7-dienyl 3,4-methylenedioxyaniline ethylN-3,7-dimethylocta-2,6-dienyl p-aminophenylketone ethylN-3,7-dimethyloct-6-enyl p-aminophenylketone ethylN-7-7-chloro-3,7-dimethyloctyl p-aminobenzoate ethylN-S-chloro-1,5-dimethylhexyl p-aminobenzoate ethylN-7-chloro-3,7-dimethylnon-2-enyl p-aminobenzoate ethylN-7-chloro-3-ethyl-7-methylnon-Z-enyl p-aminobenzoate ethylN-8-chloro-4,8-dimethylnon-3-enyl p-aminohenzoate methylN-7-chloro-3,7-dimethyloct-2-enyl p-aminophenylketone methylN-7-chloro-3,7-dimethyloctyl p-aminophenyl ketoneN-7-chloro-3,7-dimethyloct-2-enyl 3,4-methylenedioxyanilineN-7-chloro-3,Tdimethyloctyl 3,4-methylenedioxyanilineN-S-chloro-l,5dimethylhexyl 3,4-methylenedioxyanilineN-7-chloro-3,7-dimethylnon-2-enyl 3,4-methylenedioxyanilineN-7-chloro-3-ethyl-7-methylnon-2-enyl 3,4-methylenedioxyanilineN-8-chloro-4,8-dimethylnon-3-enyl 3,4-methylenedioxyaniline ethylN-7-chl0ro-3,7-dimethyloct-2-enyl p-aminophenylketonc EXAMPLE 4Anhydrous hydrogen chloride is introduced into 100 ml. of ether at C.until a saturated solution is obtained. One gram of ethylN-3,7-dimethylocta2,6-dienyl p-aminobenzoate is added to stand at 0 C.for four days. The mixture is then evaporated under reduced pressure toyield N-3,7-dichloro 3,7 dimethyloctyl p-aminobenzoate which can bepurified by chromatography.

ACTIVITY TESTS The test substances were applied externally to freshlymolted last larval instars or freshly molted pupae in a constant 1microliter drop of an acetone solution. In injection assays, the testsubstances were injected into the same developmental states in lmicroliter of olive oil. In sterilization assays on females, the testsubstances were applied externally in l microliter of acetone to twodays old females.

Evaluation of activity: The juvenile hormone activity was evaluated fromthe degree of morphological change induced, after the subsequentmolting. The effects are expressed in ID-SO activity units (halfinhibition of metamorphosis) indicating that amount of the substance inmicrograms, which under the above mentioned conditions caused formationof half-larval, half-imaginal adultoids (with Hemiptera) and half-pupal,half-imaginal adultoids (with beetles). These adultoids are completelyincapable of a further development and die. Even lower does than ID-SOvalues may lead to death of the population. The sterilization activitywas evaluated on the basis of effects on the embryonic development andhatching ability of eggs.

Table I shows the juvenile hormone activity on some insect speciespossessing both the complete and incomplete metamorphosis. The ID-50data are expressed in micrograms per specimen.

It may be seen from the table that the test substances display aconsiderably high activity; in some cases, this activity is about athousand times higher than with classical insecticides. Furthermore, thetest substances are very active when applied topically. The testsubstances belong to the group of selective pesticides since some ofthem are active only on some insect species and are inactive on theother one. This is a great advantage in comparison with classicalinsecticides which kill insects without any exception.

The test substances may be used as insect pesticides of the newgeneration, cf. C. M. Williams: Sci. Amer. 217, 13 (1967 They can beapplied in field conditions in the form of a spray, dusting, or aerosol.They may be used to contaminate insect localities and insect food. Theeffect of the test substances consists in the formation of deformedspecimens incapable of a further development or in the sterility ofeggs.

TABLE I Pyrrhoeorldae Tenebn'onidae:

Pentatomldae: Tenebrio Pyrrhocoris Dysdercus Graphosoma molitor apterusct topical topical topical Top. Inj.

I=Ethy1 N-7-chloro-3,7-dimethyloet-2-enyl paminobenzoate.

II= Ethyl N,N-bis-7-chloro-3,7-dimethyloct-2-eny1 p-arninoben zoateIII=Methy1 N-7-chloro-3,7-dimethyloctyi p-aminobenzoate.

IV=N-7-chIoro3,7-dimethyloct-2-enyi 3,4-methylenedioxyaniline.

VI=nlfilfi7,1l-d1ch1or0-3,7,ll-trimethyldodee-Z-enyl 3,4-methylenedioxyano.

Compounds I and H when applied to adult females of Pyrrhocoris (0.1-1.0microgram per specimen) caused more than 50% permanent sterility ofeggs; consequently, they belong to the best ovicides known.

What is claimed is:

1. A compound selected from those of the following formula BK 0 Rfwherein,

R is hydrogen or lower alkyl; R is one of the groups (B) or (C);

in which each of R R and R is hydrogen or lower alkyl; Z is hydrogen andZ is hydrogen, bromo, chloro, fluoro, or together with Z a carbon-carbonbond; Z is bromo, chloro or fluoro; R is hydrogen, methyl, ethyl,propyl, n-butyl or one of the groups (B) or (C); m is the positiveinteger one or two; and n is the positive integer two or three.

2. A compound according to claim 1 wherein R is the group:

R5 R1 R(. 7CH3 (CH2)n'-CH''(CH2)m a Z2 Z1 3. A compound according toclaim 2 wherein m is one and n is two.

4. A compound according to claim 3 wherein R is methyl or ethyl; each ofR R and R is methyl or ethyl and R is hydrogen.

5. A compound according to claim 4 wherein R is methyl; Z is chloro; andeach of Z and Z is hydrogen or together form a carbon-carbon bond.

6. A compound according to claim 5 wherein R is methyl.

7. A compound according to claim 5 wherein each of R and R is methyl.

8. A compound according to claim 3 wherein R is methyl or ethyl; each ofR R and R is methyl or ethyl and R is the same as R 9. A compoundaccording to claim 8 wherein R is methyl; Z is chloro; and each of Z andZ is hydrogen or together form a carbon-carbon bond.

10. A compound according to claim 9 wherein R is methyl.

11. A compound according to claim 9 wherein each of R and R is methyl.

12. A compound according to claim 1 selected from the following formula:

Z Z1 wherein, R is hydrogen or lower alkyl; R is hydrogen, methyl,ethyl, propyl, n-butyl, or a group of the formula:

and each of R R and R is hydrogen or lower alkyl;

Z is hydrogen and Z is hydrogen, bromo, chloro,

fluoro or together with Z a carbon-carbon bond; Z

is bromo, chloro or fiuoro; m is a positive integer 1 or 2 and n is apositive integer 2 or 3. i

13. The compound according to claim 1 which is ethylN-7-chloro-3,7-dimethyloct-2-eny1 p-aminobenzoate.

References Cited UNITED STATES PATENTS 3,485,865 12/1969 Richter 260-518R X ALEX MAZEL, Primary Examiner J. H. TURNIPSEED, Assistant ExaminerU.S. Cl. X.R.

